Organo bimetallic compositions



United States Patent Ce 3,033,885 ORGANO BIMETALLIC COMPOSETIONS Richard D. Gorsich, Baton Rouge, La, assignor to Ethyl Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 28, 1961, Ser. No. 106,166 4 Claims. (Cl. 260-42937) This invention relates to a novel process for the manufacture of certain useful bimetallic compounds, specifically, halo and organo halo metallic manganese carbonyl ligand compounds wherein the metals of the halo and organo halo metallic groups are members of group IV-A of the periodic system of the elements.

Heretofore, certain organic and inorganic metal carbonyls have been suggested as gasoline additives, primarily for the purpose of increasing the antiknock ratings of the gasolines. For example, manganese pentacarbonyl is a highly effective antiknock agent both when used as the sole antiknock agent and when used in combination with alkyllead antiknock compounds, e.g., tet r'aethyllead. Effective as many of these carbonyl compounds may be, however, they all exhibit certain shortcomings in use which materially decrease their value for the stated purpose. For example, their use is generally associated with more or less severe engine wear and with a shortened useful life of the exhaust valves. It is a specific and valuable property of the compounds produced by the process of this invention that they minimize these particular problems; as a result of their unusual chemical structure they do have good antiknock properties and yet they do not have the above substantial adverse effects of markedly increasing engine wear and impairing exhaust valve durability.

Accordingly, it is an object of this invention to provide a novel and effective method for the preparation of useful halo and organo halo metallic manganese carbonyl ligand compounds wherein the metals of the halo or organo halo metallic group are members of group IV-A of the periodic system of the elements. Another object is to provide a novel and effective method for the preparation of such compounds in high yield and purity. A further object is to provide a more eflicient method for producing compounds which exhibit the good antiknock effectiveness of manganese carbonyls but which are free from the marked disadvantages of shortened exhaust valve life and high engine wear associated with the use of prior metallic carbonyls in general. These and other important objects of this invention will become apparent hereinafter.

The novel process of this invention is an organic rad ical replacement process wherein a triorgano group IV-A manganese tetracarbonyl ligand compound is reacted with a halogen. The organo group IV-A metal manganese tetracarbonyl ligand reactant is represented by the general formula R M Mn(CO) ER' In this formula, M represents an element of group IV-A of the periodic system of the elements having an atomic number from 14 to 82, inclusive, i.e., silicon, germanium, tin or lead; E is an element of group V-A of the periodic system of the elements having an atomic number from 15 to 51, inclusive, i.e., phosphorus, arsenic or antimony; R is a hydrocarbon radical preferably having up to about 18 carbon atoms and R is a hydrocarbon or oxyhydrocarbon radical preferably having up to about 18 carbon atoms. The hydrocarbon radicals and the hydrocarbon portions of the oxyhydrocarbon radicals may be alike or difierent. The hydrocarbon radicals are preferably alkyl, alkenyl, aryl, cycloalkyl, aralkyl or alkaryl radicals, and the oxyhydrocarbon radicals are preferably alkyl, aryl, cycloalkyl, aralkyl or alkaryl radicals. In this process 3,033,885 Patented May 8, 1962 one or more of the hydrocarbon radicals attached to the group IV-A metal of the above describedreactant is replaced by a [halogen having an atomic number from 17 to 5 3, inclusive, i.e., chlorine, bromine or iodine. Of the carbonyl ligand reactants, triphenyltin manganese tetracarbonyl triphenylphosphine is particularly preferred because of its ease of preparation, because of its relative volatility and solubility in organic solvents which markedly facilitate its purification and reaction in the instant process, and because of the ease of synthesis of the component compounds from which it is prepared. Of the halogen reactants, chlorine is particularly preferred because of its economy and accessibility. Thus, a particular embodiment of this invention is the reaction of chlorine with triphenyltin manganese tetracarbonyl triphenylphosphine. Other embodiments will be evident as the discussion proceeds.

Illustrative of the carbonyl ligand reactants are triphenylsilicon manganese tetracarbonyl trimethylphosphine, trimethylgermanium manganese tetracarbonyl triallylarsine, triethyltin manganese tetracarbonyl tri-u-naphthylstibine, trioctyllead manganese tetracarbonyl tricetylphosphite, tricetylsilicon manganese tetracarbonyl trimesitylarsine, trivinylgermanium manganese tetracarbonyl triethylantimonite, triallyltin manganese tetracarbonyl tribenzylphosphite, tribenzylllead manganese tetracarbonyl triphenylarsenite, tricyclopentadienylsilicon manganese tetracarbonyl trivinylstibine trimesityl-germanium manganese tetracarbonyl tri-m-cumenylphosphine, tri-o-cumenyltin manganese tetracarbonyl trioctylarsine and tri-anaphthyllead manganese tetracarbonyl tricyclopentadienylantirnonite. Of these carbonyl ligand reactants, the

.triaryltin manganese tetracarbonyl ligand compounds, es-

pecially triphenyltin manganese tetracarbonyl triphenylphosphine, are preferred because of their ease of separation and because of their solubility in organic solvents which markedly facilitates their purification and reaction. The process of this invention is carried out by bringing the reactants together in the presence or absence of a solvent and generally, but not necessarily, at a moderately elevated temperature. Preferably, the reactants are combined at a temperature in the range of -B0 to 150 C. Temperatures in the range of -l0 to C. are preferred because under these conditions the reaction proceeds at a satisfactory rate, the reactants and products exhibit adequate stability, and these temperatures are within the liquid range of the preferred selected solvents if such are used. When lead compounds are employed, reaction temperatures in the rangeof -30 to 0 C. are particularly preferred, since some cleavage at the metalmetal bond of the carbonyl ligand reactant sometimes occurs at higher temperatures. The solvents employed may be either low-boiling or high-boiling depending upon the reaction temperatures and pressures desired. Thus, if the reactions are to be carried out at or near ambient temperature and at atmospheric pressure, low-boiling solvents are satisfactory, whereas if it is desired to carry out the reaction at elevated temperatures, high-boiling solvents may be used'at atmospheric pressure or low boiling solvents and elevated pressure may be used.

Typical of the lower boiling solvents which can be used are the following: toluene, ethyl benzene, chlorobenzene,

ethyl amyl ether, ethyl isoamyl ether, fl-chloroethyl ether,

fi-bromoethyl ether and bis-chloromethyl ether. Among the high-boiling solvents which may be employed are achloron-aphthalene, 18-chlorohaphthalene, 1,2 dichloronaphthalene, benzyl butyl ether, benzyl ethyl ether, butyl phenyl other, butyl-o-tolyl ether, butyl-m-tolyl ether, butylp-tolyl ether, heptyl phenyl ether and bis(p-chlorophenyl) ether.

It is preferred to use the reactants in essentially stoichiometric proportions of one equivalent of halogen per equivalent of hydrocarbon to be displaced from the group IVA metal of the carbonyl ligand compound, because problems of separation and recovery are thereby reduced, buta slight excess of one reactant or the other may be used,,if desired, to drive the reaction toward completion. Moreover, if complete replacement of the hydrocarbon groups attached to the group IV-A metal is desired, a substantial excess of halogen may be used without the occurrence of significant amounts of undesirable side reaction.

The reaction proceeds smoothly and rapidly under the prescribed conditions, reaching completion for the halogenation .of the loweralkyl and aryl derivatives in 10 minutes to /2 hour, particularly when a solvent is used. Somewhat longer reaction times are desirable for the more highly substituted aryl derivatives and for those derivatives containing'highly substituted ligands. Somewhat shorter reaction times are satisfactory for the lowest alkyl derivatives, particularlyif the reactions are carried out in the absence of solvents and of diluents for the halogen reactants. In any-event, reaction periods up to about 3 hours are quiteadequate for good yields.

The carbonyl ligand reactants can readily be prepared bythe reaction of an alkali metal manganese tetracarbonyl ligand complex Wi-than organometallic halide of a metal of group IV-A of the periodic system, i.e., silicon, germanium, tin or lead, or by the reaction of an organo groupfiIV A metal manganese pentacarbonyl with the appropriate ligand. Both reactions proceed rapidly when the components are stirred together in tetrahydrofuran solution at room temperature.

The products of the novel process of this invention are ofconsider'able value in the chemical and allied arts.

For-example, they are potent antiknock agents and in this utility. they are versatile agents in that they are highly efie'ctive in both unleaded and conventional leaded gasolines made from a Wide variety of base stocks. An additional feature of these compounds is that when they are used as antiknock agents the engine wear andexhaust valve durability characteristics of the engine are not markedlyimpaired, which is the situation brought about byzthe use of metallic carbonyls heretofore known and so employed. A further advantage of these compounds is that, owing to the presence of halogen in the compounds, the amount of halogen scavenger required to be used in the fuel along with the conventional antiknock compounds is greatlyreduced.

The invention will be more fully understood by reference to the following illustrative examples in which all parts andpercentages are by weight.

Example I Example 11 Chlorine mixed-with 2 volumes ofair as a diluent is bubbled for '1 hour'at'a temperatureof-10 C. through a solution of1.71 parts ofitrirnethyltin manganese tetraearbonyl triphenylarsenite in 77 parts'of chloroform. The

. solvent' is evaporated leaving a residue which uponrecryst-allizationfrom' benzene yields tri chlorotin manganese tetracarbonyl triphenylarsenite.

Example III To 1.45 parts of triethyltin manganese tetracarbonyl triethylstibine, dissolved in 65 parts of carbontetrachloride,

a solution of 20 parts of bromine in carbon tetrachloride 4 is added. The mixture is stirred for a half hour at 2229 C. The product obtained is tribromotin manganese tetracarbonyl triethylstibine.

Example 1V Tricyclopentadienylsilicon manganese tetracarbonyl trioctylphosphine (1.90 parts) and chlorine (0.35 part) are dissolved in 86 parts of hexane. The solution is stirred for 10 minutes at 22-28 C. 'Cyclopentadienyl dichlorosilicon manganese tetracarbonyl trioctylphosphine is ob-- tained ingood yield.

Example VI Trimesitylsilicon manganese tetracarbonyl trioctylarseni-te (2.54parts) and chlorine (0.35 part) are dissolved in 114 parts of benzene. The mixture is stirred for l'hour at 32-43 C. Mesityldichlorosilicon manganese tetracarbonyl trioctylarsenite is obtained.

Example VII When 3.06 parts of triphenylsilicon manganese tetra-. carbonyl tricetylstibine and a solution'of 0.80 part of bromine in petroleum naphtha are mixed and the mixture is heated for 2 hou rs under reflux with 138 parts of petroleum naphtha, phenyldibromosilicon manganese tetracarbonyltricetylstibine is obtained.

Example VIII A mixture of trimethylgermauium manganese tetracarbonyl tricetylphosphite (2.60 parts), bromine (0.80 part) and tetralin (117 parts) is heated to 45-52 C. for a period of 2 hours. The product is methyldibromogermanium .manganese tetracarbonyl' tricetylphosphite.

Example IX When a mixture of 1.21 parts of triethylgermanium manganese tetracarbonyl trivinylarsine, 1.27 parts of iodine and 54 parts of benzyl ethyl ether is heated at 7486 C. for a period of 2 hours, ethyldiiodogermanium manganese :tetracar-bonyl trivinylarsine is obtained in good yield.

, Example X A mixture of 2.06 parts of trioctylgermanium manganese tetracarbonyl triallylstibine, 1.27 parts of iodine and 93 parts of butyl phenyl ether is heated at -102 C. for 2 hours.- The product is octyldiiodogermanium manganese tetracarbonyl triallylstibine.

Example XI To 2.40 parts of tricyclopentadienyltin manganese tetracarbonyl tri-m-curnenylstibine, 108 parts. of di-p-chloroethyl ether and 0.40 part of bromine are added and the mixture is heated at 1131l8 C. for 2 /2 hours. The product is dicyclopentadienylbromotin manganese tetracarbonyl tri-m-cumenylstibine.

Example XIV Example XV To 1.66 parts of phenyldimethyltin manganese tetracarbonyl tricyclopentadienylarsine, 0.18 part of chlorine dissolved in 88 parts of bis-p-chlorophenyl ether is added. The mixture is heated to l43-154 C. and is maintained at that temperature for 1 hour. The product is dimethylchlorotin manganese tetracarbonyl tricyclopentadienylarsme.

Example XVI Trimethyltin manganese tetracarbonyl tricyclopentadienylantimonite (1.72 parts), ethyl-B-bromoethyl ether (88 parts) and iodine (0.64 part) are heated together for 3-hours at 6575 C. Dimethyliodolead manganese tetracarbonyl tricyclopentadienylantimonite is obtained.

Example XVII A mixture of triethylsilicon manganese tetracarbonyl trimesitylphosphine (1.68 parts), benzene (76 parts) and chlorine (5 parts) is reacted for 20 minutes at 223l C. The product is trichlorosilicon manganese tetracarbonyl trimesitylphosphine.

Example -X VIII To 3.38 parts of tricetylsilicon manganese tetracarbonyl trimesitylarsenite, 152 parts of carbon tetrachloride are added and chlorine is bubbled into the resulting solution for a half hour at 21-33 C. The product is trichlorosilicon manganese tetracarbonyl trimesitylarsenite.

Example XIX 1.95 parts of trivinylsilicon manganese tetracarbonyl tri-u-naphthylstibine is added to 88 parts of ethylene dichloride and bromine diluted with 2 volumes of methane is bubbled through the solution in the absence of light. Reaction for 1 /2 hours at 44-55 C. results in the formation of tribromotin manganese tetracarbonyl tIl-rxnaphthylstibine.

Example XX When 2.43 parts of tribenzylgermanium manganese tetracarbonyl tri-a-naphthylphosphite is mixed With 109 parts of chlorobenzene and nitrogen saturated with bromine is bubbled into the solution for 1 hour at 19-28 C., tribromogermanium manganese tetracarbonyl tri-a-naphthylphosphite is obtained.

Example XXI 2.14 parts of tricyclopentadienylgermanium manganese tetracarbonyl triS-Z-indenylarsine and 13 parts of iodine are mixed and the mixture is dissolved in 96 parts of mdichlorobenzene. The solution is stirred for 3 hours at 23-30 C. The product is triiodoger-manium manganese tetracarbonyl tris-Z-indenylarsine.

Example XXII A mixture of 3.04 parts of trimesitylgermanium manganese tetracarbonyl tris-2-fluorenylstibine and 137 parts of hexane is heated to 37-46 C. and 9 parts of iodine are added. The mixture is maintained at the above temperature for 3 hours. The product is triiodogermanium manganese tetracarbonyl tris-Z-fluorenylstibine.

The above examples have been presented by way of illustration and it is not intended to limit the scope of the invention thereby. Employing the procedures illustrated therein and the process of this invention, other products are produced by appropriate substitution of the carbonyl ligand reactants described hereinbefore. Thus, employing the process of this invention, the following products are also produced in high yield from stoichiometric proportions of the appropriate reactants: trichlorosilicon manganese tetracarbonyl tris(methylcyclopentadienyl)stibine, dibromopropylgermanium manganese tetracarbonyl tridecylarsenite, iododibutyltin manganese tetracarbonyl trivinylphosphine, tribromolead manganese tetracarbonyl triisooctylantimonite, diiodoethylsilicon manganese tetracarbonyl tridodecylarsine, chloro-bis-(Z-indenyl)germanium manganese tetracarbonyl tribenzylphosphite, triiodotin manganese tetracarbonyl tripropylstibine, dichloromesityllead manganese tetracarbonyl tri-a-naphthylarsenite, and bromodimethylsilicon manganese tetracarbonyl tris(2- fluorenyl)-phosphine. Other examples of the products obtainable in high yield by the process of this invention will be evident.

In carrying out the process of this invention, the reactants are normally combined as indicated above in approximately stoichiometric proportions but the proportions employed can vary from a percent or greater excess by weight of the halogen reactant (when a trihalo derivative is desired) to a 100 percent or greater excess of the carbonyl ligand reactant (when a monohalo derivative is desired). The amount of the excess is obviously limited to some extent by the particular product desired. A slight excess of one reactant or the other, as about 10 percent by weight, is often used to bring about an increased reaction rate. In any event, when an excess of one reactant is used the product consists of a mixture of compounds which can be separated by taking advantage of differences in solubility or other physical or chemical properties. However, the product compounds need not be separated, but can be employed as obtained in the reaction mixture.

As indicated above, the reactions of this invention are usually carried out by bringing the components together in solution. The solvents are compounds or mixtures which are essentially inert and preferably liquid under the reaction conditions. Thus, they may include essentially inert hydrocarbons such as hexane, octane, cetane, benzene and the like; halohydrocarbons such as ethyl chloride, methylene dichloride, the chlorofiuoromethanes, a-trifluorotoluene, chlorobenzene, m-dichlorobenzene and the like; ethers such as diethyl ether, di-n-butyl ether, fi-chloroethyl ethyl ether, bis-fl-chloroethyl ether, benzyl ethyl ether, benzyl butyl ether, butyl phenyl ether, butylo-tolyl ether, butyl-m-tolyl ether, butyl-p-tolyl ether, heptyl phenyl ether and bis(p-chlorophenyl)ether and the like; and mixtures of any of the foregoing. Chloroalkanes are especially preferred as solvents, particularly those containing up to six carbon atoms. The solvent of choice is methylene chloride because of its low boiling point and its relatively high solubility for the reactants (these being of particular value in that they facilitate separation of the solvent and recovery of the product) and because of its accessibility and ease of preparation.

Under some conditions, the halogen reactants are employed in the gaseous phase, and thus can simply be bubbled through the reaction mixture. However, when used in the gaseous phase, they may be mixed with inert diluents for the purpose of reducing the activity of the halogen and preventing over-halogenation. Any diluent inert to the reactants and products may be used. The compounds are stable on exposure at reaction temperature to dry nitrogen which can thus be used with safety. Other suitable diluents include dry air, carbon dioxide, low-molecular-weight gaseous hydrocarbons and the noble gases helium, neon, argon, hryston and xenon.

Because the reactions ordinarily proceed at satisfac- 7. tory rates under normal pressure conditions, atmospheric pressure is usually satisfactory but pressuresranging from 10 mil1imeters of mercury to 100 atmospheres may be used if desired, provided a liquid reaction system is maintained at least in part.

The normally solidproducts of the process are soluble in and can be purified by recrystallation from a variety of organic solvents. Specifically, simple aromatic solvents such as benzene or toluene, simple aliphatic solvents such as hexane, alcohols such as ethanol, and halohydrocarbons such as methylene chloride and carbon tetrachloride and their mixtures are satisfactory.

As stated above, the products obtained according to thisinvention are useful as antiknock agents for internal combustion engine fuels. They may suitably be employed in concentrations varyingfrom that corresponding to about 0.005 gram of manganese per gallon to their saturation concentrations at ambient temperature. They 'are highly efiective agents and their versatility is shown by the fact that theycan be added to the fuel either alone or in combination with other antiknock agents such as'tetraethyl-lead. For example, the addition of0.01 gram of manganese per gallon astrichlorolead manganese tetracar-bonyl triph'enylphosphine to a catalytically' cracked gasoline increases the octane number thereof; Similar such enhancement in the octane number of f uelsis obtained employing other products of this invention.

Furthermore, the bimetallic compoundsproduced by the process are subject to thermal decomposition at elevated temperatures, as about 150 C. and higher, so that Other uses for the products of this invention willnow.

be evident.

Having. thus described the novel process of synthesis v3.0 theycan beused toplate an alloy of the component for the bimetallic ligand compounds, it is not intended tobe limited-except as set forth in thefollowing claims:

I claim: 1. The method of preparingacompound represented by the general formula which comprises reacting a halogen having an atomic number from 17 to 53, inclusive, with a compound represented by the general formula wherein X is a halogen having an atomic number from 17 to 5 3, inclusive; M is an element selected from group IV-A of the periodic system of the elements and having consisting of hydrocarbon andoxyhydrocarbon radicals. having up to about 18 carbon atoms; and n is an integerfrom 0 to 2, inclusive.

2. The method of claim 1 wherein said halogen is chlorine.

3. The method of claim 2 wherein the reaction is carried out in a chloroalkane asa-solvent.

4. The method for producing trichlorotin manganese tetracarbonyl triphenyl phosphine which comprises're. acting a solution of triphenyltin managanese tetracarbonyl triphenylphosphine in liquid methylene chloride with an excess of elementary chlorine. 7

References Cited in the file of this patent UNITED STATES PATENTS 2,911,424 Kaufman Nov. 3, 1959 2,922,802 Kaufman Jan. 26, 1960 2,922,803 Kaufman Jan. 26, 1960 

1. THE METHOD OF PREPARING A COMPOUND REPRESENTED BY THE GENERAL FORMULA 